Polyaryl sulphide



United States Patent F 3,053,901 POLYARYL SULPHIDE Ian HendrikUhlenbrock, Weesp, Netherlands, assignor to North American PhilipsCompany, Inc-, New York, N.Y., a corporation of Delaware No Drawing.Filed June 9, 1960, Ser. No. 34,869 Claims priority, applicationNetherlands June 13, 1959 6 Claims. (Cl. 260-609) The invention relatesto the preparation of polyaryl sulphides, in particular of diarylsulphides, from an alkali compound or an aryl thiophenol and an arylchloride.

In the literature some methods are described for the preparation ofdiaryl sulphides which, however, are not suitable for practicalpurposes. It is described, for example, that in the conversion of arylbromides with lead mercaptides, Zinc mercaptides or mercury mercaptidesat 225230 C. aromatic thioethers are obtained in good yields. Forpractical purposes this method is not very attractive, also because ofthe high costprice of the bromides. It is described that aryl chloridesare not very well useful for this method owing to the slight reactivityof these compounds.

it is also described, that phenyl-iodide can be converted into athioether with a thiophenol in the presence of copper as a catalyst.

It is further described that reaction of a nitrobromo benzene and anitrobromotoluene with sodium thiophenolate results in thioethers onlywhen the bromine atom occupies the ortho-position or para-position withrespect to the nitro group; as is known, the reactivity of such abromine atom is increased by these nitro groups.

It is described in addition that 2-(2-methyl-5 halogenophenylmercapto)-4halogeno (or alkyl or alkoxy) benzoic acids can be prepared by heating a2-halogeno-4-halogeno (or alkyl or alkoxy) benzoic acid with a metalsalt of a Z-methyl-S-halogeno thiophenol in the presence of a catalyst,which are copper powder, copper halogenide and is prepared by causing toreact a compound of the formula R,,.Ar.SMe (A) with a compound of theformula Cl .Ar.R (B) in which formulae Ar may represent a phenyl radicalor naphthyl radical, Me an alkali metal and preferably sodium, R and Rchlorine atoms or lower alkyl groups or a combination thereof, x=l or 2,n is an integer numeral of from 0 to 5 and is 1 if R represents chlorineor also chlorine and m may be an integer numeral of from 0 to 5 if x=land of from 0 to 4 if x2=2.

The reaction according to the invention is to be con sideredparticularly for the preparation of diphenyl sulphides, in which R'represents chlorine and m=1, 2 or 3 and of those in which R representschlorine and n=1 or R and R in these cases both represent chlorine.

or sulphones.

3,053,901 Patented Sept. 11, 1962 The process is particularly suitablefor the preparation of 2,4,5,4'-tetrachlorodiphenylsulphide froml,2,4,5-tetrachlorobenzene and 4-chlorothiophenol-sodiumor4-chlorothiophenol-potassium. As alkyl-substituted aryl 'compounds areto be considered particularly those aryl compounds substituted by amethyl group.

Applicants have found that the yield of diaryl sulphide is favourablyinfluenced to a considerable extent by using a considerable excess ofthe reaction component of the Formula B. Favourable molar ratios of Aand B are 1:4 to 1:40 and in particular 1:6 to 1:20.

The course of the reaction and the yield of polyaryl sulphide accordingto the invention is influenced favourably by using a solvent in whichboth reaction components are soluble. As such are to be consideredmonovalent alcohols, for example cyclohexanol, ethers, for exampledioxane, dimethyl sulphoxide and tertiary nitrogen bases, and inparticular aromatic tertiary nitrogen bases, such as pyridines andquinoline. Dimethyl formamide is a particularly suitable solvent.

Example 1 123.6 g. of 4-chlorothiophenol (0.8 mol) were dissolved in 150cm. of a 30% by weight sodium methylate solution in .methanol. Thesolution was evaporated to dryness in vacuo. The residue,4-chlorothiopheno1 sodium, was dissolved in 1400 cm. dimethyl formamide,and added to a hot solution of 3600 g. of 1,2,4,S-tetrachlorobenzene (16mol) in 2600 cm? of dimethyl formamide, whilst stirring. Then theresulting mixture was refluxed for 90 minutes, Whilst stirring.Subsequently, the reaction mixture was cooled and stored at 0 C. forapproximately 16 hours. Crystallized tetrachlorobenzene and sodiumchloride were filtered Off and washed with 1000 cm. of cold dimethylformamide. The filtrate Was evaporated until approximately 90% of theused dimethylfor-mamide had been recovered. The residue was thensubjected to a steam distillation to remove traces oftetrachlorobenzene. The residue of the steam distillation was taken upin 1.5 liters of ether, filtered and washed twice with Water. Afterdrying on sodium sulphate and evaporation, the 2,4,5,4,-tetrachlorodiphenyl sulphide was obtained. Yield: 215 g. (83%); meltingpoint: approximately 84 C.

The compounds mentioned in Table I were prepared in an analogous manner.Table 11 states the starting substances (columns 2 and 3), the molarratios in which the compounds according to the Formulae B and A are used(column 4), the solvent used (column 5), the melting point and/or theboiling point of the resulting products (column 6) (the melting point isindicated by S and expressed in C., the boiling point by F and expressedin C. at the pressure used in millimetres of mercury column), and theyield of product obtained (column 7).

The products obtained according to the process of the invention oftenhave an acaricidal activity and/ or may be used as intermediates for thepreparation of acaricidal compounds. They may be converted into saidcompounds by oxidation to the corresponding sylphoxide and/ The reactionproducts may be converted into higher-chlorinated products bychlorination. For example, 2,5-dichloroand 2,5,4'-trichlorodipheny1sulphide may be chlorinated to 2,4,5,4-tetrachlorodipheny1 sulphide and2,5-dichloro-4'-methyldiphenyl sulphide to 52,4,5-trichloro-4-methyldiphenyl sulphide. The thus ob- 3 Table IProducts 2.4.5it'-tetrachlorodlphenylsulphlde.

Do. 2.5.4;5trichlorodiphenylsulphide.

Do. 2.5-dichlorodiphenylsulphlde. 2-chl0ro-4-methyldiphenylsulphlde.2.5-dichloro4-methyldiphenylsulphide.3.5-diehloro-4'-methyldiphenylsulphide.2.4.5-trichloro4-metliyldiphenylsulphide.2.S-dichloro-2.5-dimethyldiphcnylsulphide.2.ediehloro-il.4-dimethyldiphenylsulphide.2.5-dicl11or0-3.4-dimethyldiphenylsulphide.2.4.5-trich1oro-3.6.4-trimethyldiphenylsulphide.S.S-bis(4'-ch10rophenyl)-2.5-dichloropl1enylenedisulphide-IA.

4 0 to 4 when x=2 comprising, condensing a compound of the formula RArSMe wherein Me is an alkali metal with a compound of the formula ClArR 2. The method of claim 1 wherein a compound of the formula ClC H SMeis employed as a reactant.

3. The method of claim 1 wherein a compound of the formula ClArClwherein Ar is a benzene radical and m is an integer from 1 to 3, isemployed as a reactant.

4. The method of preparing 2,4,5,4 -tetrachl0rodipheny1 sulfidecomprising condensing 1,2,4,5-tetrachlorobenzene with an alkali metal4-chlorothiophenolate wherein the alkali metal has an atomic weight offrom 23 to 39.1 inclusive.

5. The method of claim 4 wherein the reaction is car- 5 ried out at atemperature of from 100 C. to 250 C. in

Phenyl-a-naphtylsulphide. lorodiphenylsulphide, a solvent selected fromthe group consistmg of dimethyl Do. amide, pyridine, qumohne, andtriethanolarnme.

6. The method of claim 4 wherein the molar ratio of Table 11 Ex.Physical constants resulting Yield No. Rn.Ar.SMe ClxALR/m BzA DiluentProducts 111 percent I 4-chl0rothiophenol-Na t.2.4.5-tetrachl0robenzeneDimethylformamiden S=ca 1. 84 O 33 11.. do (in 10 d0 S=8zr86 C..- isLII. do do 10 Pyridine-.. S=84.5- 5.5 C 65 1.2.4trlehlorobenzene.. 6-.d0. S=7-76 C- ,3 do 6 Quinol1ne.- S=7a76 C. 69 6 'IriethanolamiS=75-76 C. do 6 S=75-76 C 62 Thiophenol-Na do 6. 2 F=158-160 1.1 mm.mercury... 75 p-Thiokresol-Nam 1.2-diehlor0benzene 6.2 F=15916l C. at 1mm. mcrcury do 1.2.4-trichlorcbenzeno 6.4 S=67.5-09.5 C 521.3.5-trichlorobenzene 5.5 do

O. at 1.0 mm. mercury,S 68

XII.- do 1.2.4.5-tetraehlorobenzene 10 Dimethyl ormflrniden S=93 O 51XIIL--. 2.5dimethylthiophenoLNm. 1.2.4-trichlorobenzene... 6.3 QuinOlmeS=-61 (.2 XIV- 2.4dimethylthiophenol-Nai. 7.5 F=163166 C.at1.0mm.mereury55 XV BAdimethyIthiOphenoI-Na. do 7.8 F=19 2 O. at 0.7mm. mercury 71XVL-.. p-Thiokresol-Na 1.2.4.5-tetrach1oro-p. yl 8.5 D methylformamidenS=96 a 60 XVII..- 4-ch1orothiophen0l-Na 1.2.4.5-tetraehlorobeuzene 1.0Pyridine 8 222 C- 78 XVIIL. Thiophenol-Na a-Chlomnaphtalene 5Dimethylformamldeu S=38 0 60 XIX tehlorothiophenol-Na1.2.4.5-tetrachlorobenzene-. 20 Y l n 1---- =C=L 80 C 42 YY do do 20Dimethylsulphomdm. S=ca.80 C 45 What is claimed is:

l. A method for preparing polyaryl sulfides of the formula:(R,,.Ar.S)X.Ar.R wherein R and R are each members of the groupconsisting of chlorine and lower alkyl, Ar is a member of the groupconsisting of phenyl and naphthyl, x is a number selected from the groupconsisting of 1 and 2, n is an integer from 0 to 5, m is an integer from0 to 5 when x=1 and is an integer from the chlorinated benzene to thephenolate is from 6:1 to 20:1.

References Cited in the file of this patent UNITED STATES PATENTSGregory et a1. Sept. 4, 1956 OTHER REFERENCES Huisman et al.: Rec. Trav.Chim. 77, 103-122 (1958).

:UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3053301 September 11, 1962 Jan'Hendrik Uhlenbroek It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 1 line 65, for if x2:2" read if X Z Signed and sealed this 26thday of Febnuary 1963.

(SEAL) Attest:

ESTON Go JOHNSON DAVID L. LADD Attesting Officer Commissioner of Patents

1.A METHOD FOR REPARING POLYARYL SULFIDES OF THE FORMULA:(RN.AR.S)X.AR.R1M WHEREIN R AND R1 ARE EACH MEMBERS OF THE GROUPCONSISTING OF CHLORINE AND LOWER ALKYL, AR IS A MEMBER OF THE GROUPCONSISTING OF PHENYL AND NAPHTHYL, X IS A NUMBER SELECTAED FROM THEGROUP CONSISTING OF 1 AND 2, N IS AN INTEGER FROM 0 TO 5, M IS ANINTEGER FROM 0 TO 5 WHEN X=1 AND IS AN INTEGER FROM 0 TO 4 WHEN X=2COMPRISING, CONDENSING A COMPOUND OF THE FORMULA RNARSME WHEREIN ME IS AALKALI METAL WITH A COMPOUND OF THE FORMULA CLXARA1M.